Vanadium organophosphates

ABSTRACT

Vanadium organophosphates represented by the formula:   and polymers thereof represented by the formula:   WHEREIN X IS 2 TO 6, R is an alkyl or an alkyl ether having 1 to 6 carbon atoms or an aryl having up to 16 atoms, or mixtures thereof, CAN BE PREPARED BY A REACTION BETWEEN A VANADIUM OXIDE, OXYHALIDE, OR HALIDE OR AN ALKYL VANADATE AND A TRIALKYL, TRIALKYL ETHER OR A TRIARYL PHOSPHATE. A mixture of the vanadium organophosphate and an organoaluminum halide forms an active vanadium coordination catalyst. This catalyst is especially useful in the production of &#39;&#39;&#39;&#39;EP&#39;&#39;&#39;&#39; and &#39;&#39;&#39;&#39;EPDM&#39;&#39;&#39;&#39; rubber. A particularly effective vanadium coordination catalyst comprises vanadium (IV) oxybis (diethyl phosphate) and an organoaluminum chloride.

United States Patent [1 1 Huerta et al.

[ *Dec. 30, 1975 4] VANADIUM ORGANOPHOSPHATES [75] Inventors: James R.Huerta; Amos R.

Anderson; Jeffrey G. Meyer, all of Adrian, Mich.

[731 Assignee: Dart Industries Inc., Los Angeles,

Calif.

21 Appl. No.: 308,066

Related US. Application Data [60] Continuation-in-part of Ser. No.102,949, Dec. 30, 1970, abandoned, which is a division of Ser. No.836,169, June 24, 1969, Pat. No. 3,595,890.

[52] US. Cl...... 260/80.78; 252/429 B; 260/88.2 R; 260/88.2 E; 260/949C; 260/949 CB [51] Int. Cl. C08F 4/68; C08F 210/18; C08F 210/16 [58]Field of Search... 260/949 C, 94.9 CB, 88.2 E, 260/882 R, 80.78; 252/429B Primary Examiner-Alan Holler Attorney, Agent, or F irm-Arthur S.Collins; Bryant W. Brennan; Fred S. Valles [57] ABSTRACT Vanadiumorganophosphates represented by the for-' mula:

R OR

' and polymers thereof represented by the formula:

VIEW:

wherein x is 2 to 6, R is an alkyl or an alkyl ether having 1 to 6carbon atoms or an aryl having up to 16 atoms, or mixtures thereof, canbe prepared by a reaction between a vanadium oxide, oxyhalide, or halideor an alkyl vanadate and a trialkyl, trialkyl ether or a triarylphosphate. A mixture of the vanadium organophosphate and anorganoaluminum halide forms an active vanadium coordination catalyst.This catalyst is especially useful in the production of EP and EPDMrubber. A particularly effective vanadium coordination catalystcomprises vanadium (lV) oxybis (diethyl phosphate) and an organoaluminumchloride.

18 Claims, No Drawings VANADIUM ORGANOPHOSPHATES CROSS REFERENCE TORELATED APPLICATION This application is a continuation-in-part ofapplication, Ser. No. 102,949, filed Dec. 30, 1970, now abandoned, whichwas a division of application Ser. No. 836,169 filed June 24, 1969, nowU.S. Pat. No. 3,595,890.

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention isdirected to novel compositions of matter and processes for theirsynthesis, a novel catalyst which includes these compositions and aprocess using the cata1ysts More particularly, the invention relates tovanadium organophosphates which when combined with organoaluminum halidecompounds result in very active catalysts for the preparation ofpolymers of alpha-olefins and copolymers of alpha-olefins, andterpolymers of the alpha-olefins and a nonconjugated diene.

2. Description of the Prior Art Transition metal compounds of varioustypes have been disclosed in the prior art; see U.S. Pat. Nos.

3,113,115 and 3,297,733 and 3,361,779. Of the organometallic compoundsdisclosed, particular attention has been given to those in which thetransition metal constituent is vanadium; see U.S. Pat. Nos. 3,294,828and 3,361 ,778. Coordination catalysts containing a vanadiumorganometallic compound, e.g., vanadium tetrachlorides and vanadiumoxytrichlorides, and a compound capable of reducing the vanadium to avalance state of less than 3, such as the organoaluminum' compounds,have long been of interest for use as polymerization catalysts; see U.S.Pat. No. 2,962,451. This interest in developing novelvanadium-containing coordination catalysts is evidenced by theconsiderable number of recent patents on the subject; see, for example,U.S. Pat. Nos. 3,392,160 and 3,396,155 and 3,427,257. Particularattention has been shown in the preparation of alpha-olefin polymers,copolymers of alpha-olefins, e.g., ethylene/propylene (EP) rubber, andthe terpolymers of the alpha-olefins with the nonconjugated dienes,e.g., ethylene/propylene/diene terpolymers, (EPDM rubber). Vanadiumcoordination catalysts have been disclosed as having activity for thepreparation of EP and EPDM rubber; see U.S. Pat. Nos. 3,166,517 and3,234,383.

SUMMARY OF THE INVENTION The present invention provides a vanadiumorganophosphate composition represented by the formula:

and polymers thereof, wherein R is an alkyl or an alkyl ether having 1to 16 carbon atoms or an aryl having up to 16 carbon atoms or mixturesthereof. The polymers of this composition can be represented by theformula:

OR OR OR wherein x is 2 to 6.

This composition can be prepared by various routes as set forth below:

a. One route to this compound is to react one mole of a vanadium oxide,V 0 wherein n is 3 to 5, e.g., V 0

with at least four 'moles of trialkyl, trialkyl ether or triarylphosphate to yield the vanadium organophosphate of this invention andside-products of an alcohol, an ether and an aldehyde as represented bythe following equation:

i ROH ROR RAH If 3/2 moles of oxygen are added to the above reaction,the same reaction occurs except the side-products are water and analdehyde as in the following equation:

ll'il ii Will wherein X is chloro, bromo or iodo.

c. A third route for'the composition of this invention comprises thereaction of two moles of an alkyl vanadate with at least four moles ofthe phosphate used in route (a) to yield the vanadium organophosphateplus the same side reactants as in the route (a) as indicated by thefollowing equation:

The vanadium organophosphate compounds of this invention when combinedwith organoaluminum halide compounds in the manner described below toform vanadium coordination catalysts are especially useful in thepreparation of polymers of ethylene, propylene and similar alpha-olefinshaving the formula: R- CH=CH wherein R is hydrogen or a hydrocarbonradical, particularly an unsaturated alkyl hydrocarbon radical having 1to 8 carbon atoms, e.g., butene-l; hexenel; 4-methylpentene-l;heptene-l; 5-methylhexene- I octene-l; 4-ethylhexenel; l-nonene;l-decene, and dienes, e.g., butadiene and the like. The catalyst of thisinvention is especially useful in the copolymerization of ethylene andpropylene to yield rubbery products and the production of unsaturated,sulfur-vulcanizable, rubbery terpolymers of ethylene and propylene and anonconjugated diene, e.g., dicyclopentadiene (DCP);methylcyclopentadiene; methylene norbornene (MNB); 1,5-cyclooctadiene;1,4-hexadiene; 1,5-cyclooctadiene, or other copolymerizable dienes. Theunique features of the vanadium coordination catalysts of this inventionare high productivity of the catalyst in terms of the amount of productper pound of catalyst, low cost, ease of handling and storage, and goodsolubility and stability in solution.

PREFERRED EMBODIMENTS OF THIS INVENTION Other examples of vanadiumorganophosphate compositions of this invention include the following:

The dimer of vanadium (IV) oxybis (dimethyl phosphate):

The dimer of vanadium (IV) oxybis (di-n-butyl phosphate):

0cm, oc,H,, oc -1,, oc,H,

The dimer of vanadium (IV) oxy (diethyl phosphate) (di-n-butyl phosphateThe preferred processes for the synthesis of the vanadiumorganophosphate composition of this invention include:

a. The reaction of a vanadium oxide having the general formula V 0wherein n is 3 to 5 with an organophosphate having the general formula:

wherein R is an alkyl or an alkyl ether having I to 16 carbon atoms oran aryl having up to 16 carbon atoms at a temperature in the range ofabout 50 to 200C., at subatmospheric to about atmospheric pressure orabove for a period of hour to several days. At temperatures below 50C.,little if any reaction takes place and above 200C. the products have atendency to decompose. Although this reaction can take place under anitrogen blanket, the reaction rate and conversion increases with theaddition of oxygen. The molar ratio of the organophosphate to thevanadium oxide in the reactants is about 4:1, although the reaction canbe carried out in molar range of about lzl to 6:1. An excess amount ofthe organophosphate is generally added to keep the product in solution.

To obtain the preferred composition, 1 mole of vanadium pentoxide isreacted with at least 4 moles of triethyl phosphate at a temperature inthe range of l50 to 200C at atmospheric pressure for about 5 to 20 hourswith at least 3/2 moles of oxygen. In addition to preparing thecomposition of vanadium (IV) oxybis (diethyl phosphate), at least 4moles of acetaldehyde and 2 moles of water are produced. Further detailsof these syntheses are set forth in Examples l and 2 below.

b. The reaction of vanadium halides or oxyhalides such as VCL, and VOClwith the organophosphate, as defined under (a) above, at roomtemperature to 250C, and subatmospheric pressure for a period of /2 hourto several days.

c. The reaction of alkyl vanadates having the general formula:

H (OR):|

wherein R is an alkyl having I to 16 carbon atoms with theorganophosphate, as defined under (a) above, at room temperature to200C, and subatmospheric to atmospheric pressure for a period of /2 hourto several days.

The reaction mixture from one of the above routes is cooled, the excesssolid reactants are removed, for example, by filtration, and thefiltrate is stripped, preferably under a a vacuum to avoid decompositionof the product. The resultant impure liquid product can then besolubilized in a suitable solvent, filtered, vacuum stripped to removethe solvent and then crystallized to yield a crystalline product. Thecrystallization takes place by cooling the stripped product or by otherknown techniquesv Suitable solvents for the vanadium organophosphate ofthis invention include low boiling paraffinic hydrocarbons such aspentane, hexane, heptane and the like, or aromatics such as benzene,toluene and the like.

The vanadium coordination catalysts of this invention are obtained byusing the vanadium organophosphate composition described above with atleast one organoaluminum halide reducing compound in the presence of aninert liquid organic medium. Representative types of organoaluminumcompounds include dialkylaluminum monohalides; alkylaluminum dihalides;and aluminum alkyl, cycloalkyl or aryl sesquihalides. Particularlypreferred organoaluminum halide compounds in combination with thevanadium organophosphates of this invention include diethylaluminummonochloride and ethyaluminum sesquichloride. Other organoaluminumcompounds suitable for the coordination catalysts of this inventioninclude methyl, propyl and isobutyl aluminum chlorides. Although therelative proportions of the vanadium organophosphates and theorganoaluminum halide compounds can vary widely and one of ordinaryskill in the art can readily determine the optimum proportions forspecific vanadium and aluminum compounds by routine experimentation, onewould generally operate with an Al:V molar ratio in the range of about1:1 to 20:1. The Al:V molar ratio for the preferred vanadium andaluminum compounds, i.e., vanadium (IV) oxybis (diethyl phosphate) andethylaluminum sesquichloride or diethylaluminum monochloride, is in therange of about 4:1 to :1.

Inert liquid organic media, i.e., liquids which do not interfere withthe desired polymerization reaction, which are suitably present in thepolymerization reaction with the vanadium coordination catalysts of thisinvention include tetrachloroethylene; aromatic solvents such asbenzene, toluene, and xylenes; saturated aliphatic hydrocarbon andcycloaliphatic hydrocarbons such as cyclohexane, butane, neopentane,isopentane, n-pentane, cyclopentane, hexane, heptane, methylcyclohexane,2,2,4-trimethylpentane, octane, and nonane; chlorinated aliphatichydrocarbons; chlorinated cycloaliphatic hydrocarbons such as carbontetrachloride, ethyl chloride, methyl chloride, 1,2-dichloroethane andtrichloromonofluoromethane; and the organophosphates as described above.Particularly effective solvents for the preferred vanadium coordinationcatalyst of this invention are saturated aliphatic and cycloaliphatichydrocarbons especially n-hexane, nhcptane, cyclohexane andcycloheptane.

The vanadium coordination catalysts of this invention are employed bycontacting them with one or more of the monomers described in SUMMARY OFTHE INVENTION at subatmospheric to above atmospheric pressure and at atemperature of about -50C to 100C. Preferably the conditions forpolymerizing these monomers comprise from about atmospheric pressure toabout atmospheres and a temperature of about 5 to 50C. It has been foundfor the vanadium coordination catalysts of this invention that attemperatures above 25C the product yields tend to decrease at pressuresin the range of about 25 to 125 psig.

The polymerization reaction is arrested and the product is precipitatedout of solution by the addition of an alcohol. The product is thenwashed, filtered and dried. An antioxidant, such as butylatedhydroxytoluene, is often added to the product prior to the recovery stepto avoid its oxidation and degradation.

The polymerization reaction can either be carried out in a batch orcontinuous operation. In the continuous process, the solvent, vanadiumcoordination catalyst and monomers are continuously introduced into areaction zone which is equipped with means for agitation at a sufficientrate to provide the residence time required for the desired polymerconcentration in the reaction zone effluent.

The vanadium coordination catalysts of this invention are especiallyuseful in the preparation of EP and EPDM rubbers. The ethylene contentof these rubbery products ranges from between about 20 and weightpercent and correspondingly, the propylene content ranges from between30 and weight percent. In the case of EPDM, the amount of diene shouldexceed 1 weight percent of the final product and preferably rangesbetween about 3 and 30 weight percent. Accordingly, the ethylene andpropylene in the final terpolymer ranges between about 70 and 97 weightpercent.

The foregoing EP and EPDM rubbers are prepared by reacting, preferablyin the presence of hydrogen or other known chain transfer agents, amonomeric mixture of ethylene and propylene comprising from about 20 to70 weight percent ethylene and 30 to 80 weight percent propylene and, inthe case of EPDM, the nonconjugated diene in a reaction zone in thepresence of an inert solvent at a temperature of 5 to 50C. with acatalytic amount of the vanadium coordination catalyst of thisinvention.

The examples below illustrate the methods of preparation of thecompositions of the present invention and their use in polymerization.

EXAMPLE 1 PREPARATION OF VANADIUM (IV) OXYBIS (DIETHYL PHOSPHATE) FROMVANADIUM PENTOXIDE Vanadium (IV) oxybis (diethyl phosphate) was preparedby charging 91.0 grams of (0.5 mole) of triethyl phosphate to aglass-bowl reactor equipped with a heating mantle, stirrer, and watercondenser and then adding 18.2 grams (0.1 mole) of finely powderedvanadium pentoxide. The reactants were heated at reflux temperatures,i.e., about C. at atmospheric pressure for 7 hours. Gas chromatographicanalysis of the condensation of the effluent gases revealed that ethylether, acetylaldehyde and ethyl alcohol were produced as side productsduring the synthesis reaction. After the resulting product mixture wascooled to room temperature and the excess vanadium pentoxide filteredoff, the filtrate, which was dark green in color, was analyzed and foundto contain 5.2 weight percent vanadium.

This represented a conversion of 35 percent of the vanadium in thereaction mixture to the desired product.

About 30 grams of the excess triethyl phosphate was stripped under 10 mmHg vacuum from the product mixture. 250 ml of n-heptane were added tothe green syrup residue and the residual triethyl phosphate was strippedat atmospheric pressure with the heptane solvent. Another addition of250 ml of heptane and solvent stripping at atmospheric pressurecompleted the removal of the excess triethyl phosphate. Upon setting twodays in an evaporating dish open to the air, a green solid crystallizedfrom the syrup. The green solid was then solubilized in n-heptane andfiltered removing a TABLE I ELEMENTAL ANALYSIS OF VANADIUM (IV) OXYBIS(DIETHYL PHOSPHATE) ELEMENT ACTUAL, WT. THEORETICAL, WT.

C 27.20 1*: 0.3 25.75 35.35 i 3.0 38.59 H 5.82 i 0.3 5.40 V l3.67i0.313.65 P 16.90 0.3 16.61

An analysis of the alkoxy groups indicated the following:

ALKOXY GROUP ACTUAL, WT. THEORETICAL, WT.

OC H 50.65 i 0.5 48.302

TEMP., C. TYPE OF REACTION 31 Irreversible 79 Reversible I60Irreversible 264 Total decomposition The lowest peak of the DTA indicatethat solvent was retained in the crystals on recrystallization. It wasfound that this lowest peak could be eliminated by threerecrystallizations from n-heptane followed by ethylene glycol extractionand drying under a vacuum of mm. Hg and the 3 recrystallizations fromchemically pure n-hexane.

The molecular weight was determined of the above crystals from materialpurified by the ethylene glycol extraction and recrystallizationsdescribed in the above paragraph followed by drying under a high vacuumat ambient temperature. A 1 gram of the light blue crystals of thevanadium compound and 1 gram of naphthalene, which had beenrecrystallized from alcohol, were each separately reduced to a finepowder using an agate mortar and pestle. 0.049 grams of the light bluepowder were weighed into a glass via] to which were added 0.2337 gramsof the powdered naphthalene. The mixture was packed into a capillarytube and melted to a light blue liquid and then cooled to an opaquesolid. The resulting opaque solid inthe tube and a sample of purenaphthalene powder in another capillary tube were placed in a MettlerFPI Melting Apparatus. Each sample was heated at a rate of 0.2C/min. andthe melting points were found to be 78.6C and 804C for the opaque solidand pure naphthalene, respectively. The molecular weight of the vanadiumorganophosphate compound was calculated from the known freezing pointdepression constant, k for naphthalene, i.e., 69.0C/gm. mole/ gms., bythe following equation:

Vcompound Wt. A, H100) (Naphthalene Wt.) A T From the theoreticalmolecular weight of the vanadium organophosphate compound of 373.15 inthe formula for this compound is about 2. This tends to indicate thatthe proposed molecular structure of the vanadium compound exists as adimer in the aromatic solvent naphthalene and can be represented by thefollowing structure:

The molecular weight of the crystals were also determined using themethod described above at other concentrations of the vanadiumorganophosphate in the solvent and using diphenyl as a solvent in placeof naphthalene. The calculated value for x ranged from 1.9 to 2.2.

A comparison was made of the infrared spectrum of the vanadium (IV)oxybis (diethyl phosphate) material dispersed in petrolatum with thespectra of liquids of triethyl phosphate, triethyl vanadate and ethylpyrophosphate and with the spectrum of phosphorus pentoxide alsodispersed in petrolatum. The comparison lent further support for theproposed dimer structure. The vanadium compound absorbed very weakly inthe 1265 cm. band assigned in the literature to the phosphoryl groupindicating its absence which is in agreement with the proposedstructure. Some absorption of the vanadium compound at 1220 cm. whichwas common to that of phosphorus pentoxide compound is an indication ofsome mode of vibration of the tetrahedral-oxygen group which occurs inboth of the compounds.

Other infrared absorption bands which were common to the known compoundsand the vanadium 0rganophosphates are:

l000 cm.

I 100 cm.

Nuclear magnetic resonance (NMR) measurements of the pure vanadiumorganophosphate compound were not feasible due to the paramagneticnature of the vanadium atoms. However, hydrolysis and extraction of thevanadium by using hydrochloric acid enabled NMR examination of thehydrolyzed fragments in a deuterated chloroform solution. Thisexamination indicated ethoxylated phosphorus which verified the presenceof ethoxy groups on the phosphorus as in the proposed structure ratherthan on the vanadium.

About 1 gram of the pure compound of this example was soluble in 1 ml.each of methanol, acetone, ethylene glycol, propylene oxide, carbontetrachloride, methylene chloride and benzene. About 1 gram of thecompound was soluble in 10 ml. of n-hexane and was soluble in ml. ofwater. The high solubility of the compound in nonpolar solvents is inagreement with the nonpolar nature of the proposed structure.

Other unique properties of the vanadium organophosphate compound inaddition to its high solubility in nonpolar solvents is its stabilityboth in its solid state and in aqueous solutions.

EXAMPLE 2 PREPARATION OF VANADIUM (IV) OXYBIS (DIETHYL PHOSPHATE) FROMVANADIUM PENTOXIDE WITH AN EXCESS OF OXYGEN Vanadium (IV) oxybis(diethyl phosphate) was prepared by charging 18.2 grams (0.1 mole) offinely divided vanadium pentoxide and 182 grams (1 mole) of triethylphosphate to a glass-bowl reactor equipped with a condenser, stirrer anda means for adding air. Air was bubbled into the reactants during theentire reaction. The reactants were heated at reflux temperatures ofabout 180C. and atmospheric pressure for 4 hours. After the resultingproduct mixture was cooled to room temperature and grams of the excessvanadium pentoxide was filtered off, representing 45 percent by weightconversion of the vanadium in the reaction mixture to the desiredproduct, the filtrate was vacuum stripped at 10 mm Hg. and 130C. Thestripped liquid was cooled to room temperature, 200 ml. of benzene wereadded and the solution was heated to 50C. for 1 hour. The resultingmixture was filtered, the filtrate was vacuum stripped at 10 mm Hg. and120C, and a thick blue syrup was formed. The syrup was cooled to roomtemperature and 150 ml. of n-hexane were added to the syrup toprecipitate out the product, over a 2 hour period. 23.3 grams of lightblue solid product were recovered after filtration and after the bluesyrup was evaporated to 10 ml. Additional product was crystallized fromthe remaining 10 ml. of syrup on standing for 2 days. The product wasfound to be soluble in n-hexane and benzene and to be identical to theproduct produced by Example 1.

This Example indicates that the use of an excess of oxygen during thesynthesis reaction resulting in an increase in the conversion andreaction rate.

EXAMPLE 3 USE OF VANADIUM (IV) OXYBIS (DIETHYL PHOSPHATE) OF EXAMPLE IIN THE PREPARATION OF EP RUBBER AT 25C A stirred glass-bowl reactor wascharged with 30 psi of ethylene, 1300 cc of heptane and 320 cc of liquidpropylene. During the course of the reaction, 0.31 grams of the vanadium(IV) oxybis (diethyl phosphate) obtained from Example 1 dissolved in 30cc of benzene and 1.2 grams of ethylaluminum sesquichloride dissolved in30 cc of n-heptane were continuously metered into the reactor. Thereaction mixture was maintained at a temperature of 25C. and a constantpressure of 60 psig with a gas mixture comprising 60 mole percentethylene and 40 mole percent propylene. The reaction was terminated andthe ethylene/propylene copolymer was precipitated out of solution by theaddition of an excess amount of isopropyl alcohol after a 10 totalreaction time of 35 minutes. The resulting copolymer product wasfiltered, dried and weighed. The yield of the copolymer product was 106grams. The EP rubber product was analyzed to contain 61 mole percent(45.4 weight percent) ethylene.

EXAMPLE 4 USE OF VANADIUM TETRACHLORIDE IN THE PREPARATION OF EP RUBBERAT 25C AS A CONTROL A control run was made at the identical operatingconditions as described above, except that in place of the vanadiumorganophosphate catalyst component of this invention, vanadiumtetrachloride (VCI was employed in an amount of 0.16 grams dissolved in30 cc. of benzene. The difference in the amount of the vanadiumorganophosphate employed versus that of the vanadium tetrachloride wasthe amount necessary to put the two catalysts on the basis of equivalentvanadium contents. The yield of the copolymer product for the controlrun was 118 grams.

EXAMPLE 5 USE OF VANADIUM (IV) OXYBIS (DIETHYL PHOSPHATE) OF EXAMPLE 1IN THE PREPARATION OF EP RUBBER AT 40C Example 3 above was repeatedexcept that the reaction temperature was increased to 40C. The yieldwhen operating with the catalyst of this invention was 37 grams.

EXAMPLE 6 USE OF VANADIUM (IV) OXYBIS (DIETHYL PHOSPHATE) OF EXAMPLE 1IN THE PREPARATION OF EPDM RUBBER IN BATCH RUN A stirredglass-bowlreactor was charged with 30 psi of ethylene, 3 psi of hydrogen, 1300 ccof n-heptane and 320 cc of propylene. The temperature of the reactantswas raised to 25C and 0.31 grams of the vanadium organophosphatecompound prepared in the manner of Example 1 dissolved in 30 cc ofbenzene and 1.2 cc of ethylaluminum sesquichloride dissolved in 30 cc ofn-heptane and 8.0 cc of ethylidenenorbornene (ENB) dissolved in 30 cc ofn-heptane were added over a one half hour period. The reaction wascontinued for an additional 10 minutes after the catalyst and ENB andhad been added to the reactor. The reaction product was coagulated bythe addition of an excess amount of isopropyl alcohol containing 0.2weight percent Ionol (butylated hydroxy toluene). The coagulated EPDMrubber was separated from the liquid and then reduced to a filterablecrumb rubber by treatment in a Warring blender in the presence ofisopropyl alcohol containing the lonol. The resulting crumb rubber wasseparated from the alcohol by filtration to yield 74 grams of product.The EPDM rubber product was analyzed to contain 53.7 weight percentethylene, 36.4 weight percent propylene and 9.9 weight percent ENB. Thisyield corresponds to a productivity of 239 grams of product per gram ofthe vanadium organophosphate catalyst of this invention or about 1560grams of product per gram of vanadium content of the catalyst.

EXAMPLE 7 USE OF VANADIUM (IV) OXYBIS (DIETHYL PHOSPHATE) OF EXAMPLE 1IN THE PREPARATION OF EPDM RUBBER IN A CONTINUOUS RUN A feed vessel wascharged with 2250 cc of n-heptane and 0.70 grams of ethylaluminumsesquichloride. A glass-bowl reactor was flushed with ethylene andcharged with 30 psi of ethylene, 750 cc of the mixture from the feedvessel and 300 cc of liquid propylene. A continuous feed stream of ENBdissolved in 30 cc of n-heptane and the vanadium organophosphatecompound prepared in the manner of Example 1 dissolved in 30 cc ofbenzene were continuously added during the course of this continuous runin the presence of hydrogen at a pressure of 100 psig and a temperatureof 25C. After a 30 minute initiation period, the liquid 12 dark bluewith an increase in viscosity. After cooling to room temperature, 50.3grams of a blue solid containing 1 1.5 weight percent vanadium (5.8weight percent of the product was vanadium in the pentavalent state) and1.3 weight percent chloride was recovered. The resulting blue solid wasinsoluble in n-heptane, but highly soluble in benzene and toluene. Onrecrystallization from toluene, the resulting green crystals resembledthe monoclinic crystals of the vanadium organophosphate recovered viathe route of Example 1. The comparison of crystals was made by a studyof the photomicrographs of the crystals from the two synthesisprocedures. The crystals were found to have the elemental analysis setforth in Table III below:

TABLE III ELEMENTAL ANALYSIS OF VANADIUM (IV) OXYBIS (DIETHYL PHOSPHATE)FROM VANADIUM OXYTRICHLORIDE level in the reactor was maintained at 1300cc by slowly ELEMENT ACTUAL THEORETICAL discharging the contents. 8 3 3ZThe total reaction time for the continuous run was 90 H 2,13 3 minutes.The total feed added during this period and V 15.34 13.65 the resultingEPDM rubber properties are indicated in E 8'33 8'35 Table 11 below:10000 10000 Calculated by difference. TABLE II Total Feed Vanadiumorganophosphate compound 0.137 grams Ethylaluminum sesquichloride 0.70grams Hydrogen 9.0 liters Ethylene 108. liters Propylene 900. ccEthylidene Norbornene 18. cc n-he ane 2250 cc EPDM Product PropertiesProductivity 580 grams product/grams catalyst Ethylene 56.7 wt.Propylene 30.0 wt. Ethylidene Norbornene 13.3 wt. Iodine Number 28.1Mooney viscosity 150. ML (1+4) Gels 0.1 wt.

EXAMPLE 8 EXAMPLE 9 PREPARATION OF VANADIUM (IV) OXYBIS (DIETHYLPHOSPHATE) FROM VANADIUM OXYTRICHLORIDE 2 VOCL,

After cooling the resulting product mixture and separating it into twophases, the dark brown phase was heated for minutes at 160C. About 2grams of a clear distillate were collected during the reaction. The darkbrown mass during this heating step changed to USE OF VANADIUM (IV)OXYBIS (DIETHYL PHOSPHATE) OF EXAMPLE 8 IN THE PREPARATION OF EP RUBBERThe same procedure was followed in this example that was followed inExample 3 except that 0.44 grams of the vanadium organophosphatecompound of Example 6 was used. The yield of EP rubber product was 89grams at 25C and 55 grams at 40C.

EXAMPLE l0 PREPARATION OF VANADIUM (IV) OXYBIS (DIETHYL PHOSPHATE) FROMTRIETHYL VANADATE This method for preparing the vanadium organophosphatecompound of this invention comprised adding ml. of triethyl phosphateand 5 ml. of triethyl vanadate and reacting by heating the solution from55C. to a range of about C to C. at atmospheric pressure for a period ofabout 3 /z hours. During this period the solution charged from aninitial color of light orange to a final color of dark green similar tothe color of the reaction product of Example 1. As in Example 1, thesolid residue after removing the liquid product was light green incolor. However, because of the unstability of the product produced bythis method, none of the material extracted by benzene could becrystallized into the blue crystals characteristic of the vanadiumorganophosphate of this invention. The benzene solution of the compoundhad a vanadium content of 1 weight percent.

EXAMPLE 1 1 USE OF VANADIUM COMPOUND OF EXAMPLE IN THE PREPARATION OF EPRUBBER The procedure of Example 3 was carried out in this example exceptthat 5.5 grams of the benzene solution containing the vanadium compoundprepared via Example 10 were used. Only trace amounts of EP rubberproduct were produced at 25C.

EXAMPLE 12 PREPARATION OF VANADIUM (IV) OXYBIS (DIMETHYL PHOSPHATE) Intoa reactor equipped as in Example 1, 280.0 grams (1.82 moles) oftrimethyl phosphate and 18.2 grams (0.1 mole) of vanadium pentoxide werereacted for 15 hours at a temperature in the range of 145 to 195C underatmospheric pressure. The resulting dark green phosphate was filteredleaving 10.7 grams of unreacted vanadium pentoxide. The liquid phase wasstripped at 90C and 10 mm. Hg vacuum, resulting in 55.6 grams of bluecrystalline solid. The solid was insoluble in n-heptane, but soluble inbenzene. Blue-green prismatic crystals were formed on a singlerecrystallization from the benzene solution and were found to have theelemental analysis set forth in Talbe IV below:

TABLE IV ELEMENTAL ANALYSIS OF VANADIUM (1V)OXYB1S (DIMETHYL PHOSPHATE)Calculated by difference.

An infrared analysis was made on the crystals from this Example. Thespectrum illustrated some absorption of the vanadium compound at 1220cm. which appears to be characteristic of the vanacium organophosphatecompositions of this invention.

EXAMPLE 13 USE OF VANADIUM COMPOUND OF EXAMPLE 12 IN THE PREPARATION OFE? RUBBER The procedure of Example 3 was again followed here except 0.45grams of the vanadium (IV) oxybis (dimethyl phosphate) of Example 12dissolved in 30 cc. of benzene were used. The yield of EP rubber productwas 90 grams at 25C. and 31 grams at 40C.

EXAMPLE 14 USE OF THE VANADIUM COMPOUND OF EXAMPLE 1 IN THE PREPARATIONOF POLYETHYLENE A stirred glass-bowl reactor was charged with 210 gramsof n-heptane, 0.48 grams of diethylaluminum chloride dissolved in 30 cc.of n-heptane and 0.13

grams of the vanadium (IV) oxybis (diethyl phosphate) of Example 1dissolved in 30 cc. of benzene. Ethylene was introduced into the reactorand the reactor was maintained at a temperature of 57C. and a constantethylene gas pressure of 20 psig. At the end of 2 hours 28.0 grams ofpolyethylene were obtained. This yield corresponds to a productivity of215 grams of polymer product per gram of the vanadium organophosphatecatalyst of this invention.

EXAMPLE 15 PREPARATION OF VANADIUM (IV) OXYBIS (DI-META-TOLYL PHOSPHATE)In the reactor equipped as in Example 1, grams (0.271 moles) oftri-meta-tolyl phosphate [(CH C I-I O) PO] and 2.0 grams (0.011 moles)of vanadium pentoxide were heated from 25C to 360C in 1 hour and reactedat a temperature of 345 to 360C and atmospheric pressure for 3 hours.The reaction product was cooled to 50C. A brown syrupy product wasrecovered which was soluble in benzene but insoluble in n-hexane.

EXAMPLE 16 PREPARATION OF VANADIUM (1V) OXYBIS (DIBUTYL PHOSPHATE) Intothe reactor equipped as in Example 1, 100 grams (0.4 mole) of tributylphosphate and 10 grams (0.055 mole) of vanadium pentoxide were reactedfor 5 hours at a temperature in the range of 175 to 185C and atmosphericpressure.

After a 3 hour period at to C and 10 mm Hg vacuum, the reaction washeated at 175C and atmospheric pressure for an additional 1 hour period.For 5 minutes of this period, the temperature was increased to 250Ccausing the reaction mixture to become black and foamy indicating thatsome decomposition of product had taken place. The reaction product wasfiltered to remove 8 grams of black residue leaving a green filtrate.The filtrate was vacuum stripped under a 10 mm Hg vacuum and C to yielda green syrup which was completely soluble in n-hexane, petroleumether,' and methylene chloride. A green crystalline solid was recoveredby evaporating the syrup in air to dryness and adding 6 drops ofn-hexane per 5 grams of solid product. The resulting paste was filteredunder vacuum for 1 hour until the product was substantially dry. Thegreen solid product was found to contain 9.5 weight percent vanadium(10.5 percent theoretical) and l 1.9 weight percent phosphorus (12.8percent theoretical).

An infrared spectrum indicated the same characterised adsorption peak at1220 cm. prevalent in the other species of the organophosphatecompositions of this invention.

The foregoing examples have illustrated various methods for thesynthesis of the novel compositions of this invention as well as theirutility for use in polymerization catalysts.

While the theory behind the heretofore described processes is not fullyunderstood, the following discussion of processes of the invention isincluded in the interest of adding to the understanding of theinvention.

X-ray investigations have revealed two crystal forms for the vanadiumorganophosphates prepared in accordance with the foregoing examples. Thefirst is a tri' clinic cell of three dimers and the second is a monoclinic cell of six dimers. The triclinic cell appears to be formed by atriad of dimers bonded on the edges of the tetrahedral dimers while themonoclinic cell appears to contain two triad chains of face-coupledtetrahedral dimers.

The procedure of Example 2, in which an excess of oxygen is employedduring the synthesis operation, produces monoclinic crystals which aresoluble in both benzene and n-heptane; and the procedure of Example 1 inwhich no excess of oxygen is employed during the synthesis operation,but in which crystallization is brought about by evaporating from a dishopen to the air, over a two day period also produces monoclinic crystalswhich are highly soluble in benzene and other nonpolar solvents.

The procedure of Example 8, in which no excess of oxygen is employedduring the synthesis operation, produces a product which is insoluble inn-heptane but highly soluble in benzene and toluene as is characteristicof triclinic crystal. Recrystallization of this product from toluene,results in the formation of monoclinic crystals. Similarly, tricliniccrystals can be produced by the procedure of Example 1, if thecrystallization takes place in the absence of air, and/or is rapid.

The procedures of Examples 12 and 15, in which no excess of oxygen isemployed, are also noted to produce products which are insoluble inn-hexane, as is characteristic of the triclinic crystal structure.

What is claimed is:

1. A catalyst composition comprising a vanadium organophosphate compoundhaving the formula:

wherein R is methyl, ethyl, propyl, butyl or mixtures thereof and x is 2to 6 and an organoaluminum halide wherein the molar ratio of Al/V insaid catalyst composition is in the range of 1:1 to :1.

2. The catalyst composition of claim 1 wherein x is 2.

3. The catalyst composition of claim 1 wherein said organoaluminumhalide is a dialkylaluminum monohalide.

4. The catalyst composition of claim 3 wherein said dialkylaluminummonohalide is diethylaluminum monochloride.

5. The catalyst composition of claim 1 wherein said organoaluminumhalide is ethylaluminum sesquichloride.

6. A process for preparing polymers of at least one alpha-olefin whichcomprises reacting said alpha-olefin in the presence of an inert solventat a temperature of about 50 to 100C containing a catalytic amount ofthe catalyst composition of claim 1.

7. The process of claim 6 wherein said alpha-olefin is ethylene,propylene or mixtures thereof.

8. A process for preparing a polymer which comprises reacting a mixturecomprising about to 99 percent by weight of at least one alpha-olefinand about 1 to 30 percent by weight of at least one nonconjugated dienein the reaction zone in the presence of an inert solvent at atemperature of about 5 to 50C containing a catalytic amount of thecatalyst composition of claim 1.

9. A process for preparing a terpolymer of ethylene/- propylene/dienemonomers which comprises reacting a monomeric mixture comprising fromabout 20 to about 70 parts by weight of ethylene, from about 30 to aboutparts by weight of propylene and from about 1 to about 30 parts byweight of a nonconjugated diene in a reaction zone in the presence of aninert solvent at a temperature of about 5 to 50C containing a catalyticamount of the catalyst of claim 1.

10. A catalyst composition comprising a vanadium organophosphatecompound represented by the formulas:

wherein x is 2 to 6, or mixtures thereof and an organoaluminum chloridewherein the Al:V molar ratio is in the range of about 4:1 to 10:1.

11. The catalyst composition of claim 10 wherein the second formulapredominates and x is 2.

12. The catalyst composition of claim 10 wherein said organoaluminumchloride is ethylaluminum sesquichloride.

13. A process for preparing an ethylene/propylene copolymer whichcomprises reacting a monomeric mixture comprising from about 20 to 70weight percent ethylene and from 30 to about 80 weight percent propylenein a reaction zone in the presence of an inert solvent at a temperatureof about -5 to 50C containing a catalytic amount of the catalystcomposition of claim 10.

14. A process for preparing a terpolymer of ethylene/propylene/dienemonomers which comprises reacting a monomeric mixture comprising fromabout 20 to about 70 parts by weight of ethylene, from about 30 to about80 parts by weight of propylene and from about 1 to about 30 parts byweight of a nonconjugated diene in a reaction zone in the presence of aninert solvent at a temperature of about -5 to 50C containing a catalyticamount of the catalyst composition of claim l1.

15. The catalyst composition of claim 2 wherein said organophosphatecompound has been crystallized from a hydrocarbon solvent before beingcombined with said organoaluminum compound.

18 aluminum compound.

18. The catalyst composition of claim 16 wherein said organophosphatecompound has been further purified by filtration and recrystallizationfrom a hydrocarbon solvent before being combined with saidorganoaluminum compound.

1. A CYATALYST COMPOSITION COMPRISING A VANADIUM ORGANOPHOSPHATECOMPOUND HAVING THE FORMULA:
 2. The catalyst composition of claim 1wherein x is
 2. 3. The catalyst composition of claim 1 wherein saidorganoaluminum halide is a dialkylaluminum monohalide.
 4. The catalystcomposition of claim 3 wherein said dialkylaluminum monohalide isdiethylaluminum monochloride.
 5. The catalyst composition of claim 1wherein said organoaluminum halide is ethylaluminum sesquichloride.
 6. Aprocess for preparing polymers of at least one alpha-olefin whichcomprises reacting said alpha-olefin in the presence of an inert solventat a temperature of about -50* to 100*C containing a catalytic amount ofthe catalyst composition of claim
 1. 7. The process of claim 6 whereinsaid alpha-olefin is ethylene, propylene or mixtures thereof.
 8. Aprocess for preparing a polymer which comPrises reacting a mixturecomprising about 70 to 99 percent by weight of at least one alpha-olefinand about 1 to 30 percent by weight of at least one nonconjugated dienein the reaction zone in the presence of an inert solvent at atemperature of about -5* to 50*C containing a catalytic amount of thecatalyst composition of claim
 1. 9. A process for preparing a terpolymerof ethylene/propylene/diene monomers which comprises reacting amonomeric mixture comprising from about 20 to about 70 parts by weightof ethylene, from about 30 to about 80 parts by weight of propylene andfrom about 1 to about 30 parts by weight of a nonconjugated diene in areaction zone in the presence of an inert solvent at a temperature ofabout -5* to 50*C containing a catalytic amount of the catalyst ofclaim
 1. 10. A catalyst composition comprising a vanadiumorganophosphate compound represented by the formulas:
 11. The catalystcomposition of claim 10 wherein the second formula predominates and x is2.
 12. The catalyst composition of claim 10 wherein said organoaluminumchloride is ethylaluminum sesquichloride.
 13. A process for preparing anethylene/propylene copolymer which comprises reacting a monomericmixture comprising from about 20 to 70 weight percent ethylene and from30 to about 80 weight percent propylene in a reaction zone in thepresence of an inert solvent at a temperature of about -5* to 50*Ccontaining a catalytic amount of the catalyst composition of claim 10.14. A process for preparing a terpolymer of ethylene/propylene/dienemonomers which comprises reacting a monomeric mixture comprising fromabout 20 to about 70 parts by weight of ethylene, from about 30 to about80 parts by weight of propylene and from about 1 to about 30 parts byweight of a nonconjugated diene in a reaction zone in the presence of aninert solvent at a temperature of about -5* to 50*C containing acatalytic amount of the catalyst composition of claim
 11. 15. Thecatalyst composition of claim 2 wherein said organophosphate compoundhas been crystallized from a hydrocarbon solvent before being combinedwith said organoaluminum compound.
 16. The catalyst composition of claim11 wherein said organophosphate compound has been crystallized out in amonoclinic form before being combined with said organoaluminum compound.17. The catalyst composition of claim 15 wherein said organophosphatecompound has been further purified by filtration and recrystallizationfrom a hydrocarbon solvent before being combined with saidorganoaluminum compound.
 18. The catalyst composition of claim 16wherein said organophosphate compound has been further purified byfiltration and recrystallization from a hydrocarbon solvent before beingcombined with said organoaluminum compound.